JPWO2013191029A1 - Porphyrazine dye and use thereof - Google Patents

Abstract

The following formula (1) [in formula (1), M represents a metal atom, a metal oxide, a metal hydroxide, or a metal halide, or a hydrogen atom, and rings A, B, C, and D are independent of each other. Wherein X is a lower alkyl group, a lower alkoxy group, an amino group, a nitro group, a halogen, and the following formulas (2) to (8) (excluding those in which A, B, and C are all the above formula (8)): Represents a group, a hydroxy group, a carboxy group, a sulfonic acid group, a sulfonamide group, Y is a divalent bridging group, Z is a hydrogen atom on the nitrogen atom of a sulfonic acid group, a carboxy group, or a primary or secondary amino group. Represents a residue excluding at least one, or a residue excluding at least one hydrogen on a nitrogen atom of a heterocyclic ring containing nitrogen, wherein a and b are both average values, and a and b are each 0 12 or less, and the sum of a and b is 0 or more and 12 or less. In porphyrazine IroHata and dye dispersion composition comprising the same it is represented.

Description

The present invention relates to a novel porphyrazine dye that exhibits excellent absorption in a specific near-infrared region, has high transmittance in the visible light region, and does not impair the design properties, and uses thereof.

From the viewpoint of energy saving and global environmental problems in recent years, it is required to reduce the load on air conditioning equipment. For example, in the field of houses and automobiles, there is a heat ray shielding glass in which a heat ray shielding material capable of shielding heat rays from sunlight is applied to the window glass, and it is known that it is effective in suppressing temperature rise in the room or in the car. A near-infrared absorbing dye is used as the heat ray shielding material.
When this heat ray shielding material is applied to window glass of houses and automobiles, it has high visible light transmittance from the viewpoint of ensuring visibility, high heat ray shielding ability from the viewpoint of energy saving and global environmental problems, outdoor use However, high durability that can withstand is desired. Further, from the viewpoint of design properties, it is desirable that it is as colorless and transparent as possible or lightly colored.
In Patent Document 1, a porphyrazine dye is disclosed as a heat ray shielding material excellent in transparency. However, as a result of the study by the present inventors, the dye described in Patent Document 1 has high visible light transmittance and excellent heat ray shielding properties, but has a strong yellowish color and significantly impairs the design properties. It was difficult to use.

Japanese Patent Laid-Open No. 9-263717

The present invention has been made in view of the situation as described above, and an object of the present invention is to provide a porphyrazine dye having high visible light transmittance and excellent heat ray shielding properties. Another object of the present invention is to provide a porphyrazine coloring matter that suppresses yellowishness, has an improved utility value in the industry, without impairing the design properties in the fields of housing and automobiles, and a heat ray shielding composition containing the coloring matter.

As a result of intensive studies, the present inventors have solved the above-mentioned problem by a specific porphyrazine dye represented by the following formula (1) or a dye-dispersed composition containing the same. And the present invention has been completed.
That is, the present invention provides (1) a porphyrazine dye represented by the following formula (1):

［式（１）中、Ｍは金属原子、金属酸化物、金属水酸化物、若しくは金属ハロゲン化物、又は水素原子を表し、環Ａ、Ｂ、Ｃは、それぞれ独立して下記式（２）〜（８）

[In formula (1), M represents a metal atom, a metal oxide, a metal hydroxide, or a metal halide, or a hydrogen atom, and rings A, B, and C are each independently represented by the following formulas (2) to (8)

（ただしＡ、Ｂ、Ｃがすべて上記式（８）であるものを除く）であり、上記式（２）〜（８）中の＊は結合部位を示し、Ｘは低級アルキル基、低級アルコキシ基、アミノ基、ニトロ基、ハロゲン基、ヒドロキシ基、カルボキシ基、スルホン酸基、スルホンアミド基を表し、Ｙは二価の架橋基を、Ｚはスルホン酸基、カルボキシ基、第１〜２級アミノ基の窒素原子上の水素の少なくとも１つを除いた残基、又は窒素を含む複素環の窒素原子上の水素の少なくとも１つを除いた残基を表し、ａ及びｂはいずれも平均値であり、ａ、ｂはそれぞれ０以上１２以下、かつ、ａとｂとの和は０以上１２以下である］、
（２）式（１）中の環Ａ、Ｂ、Ｃがそれぞれ式（２）、式（４）または式（８）である（１）に記載のポルフィラジン色素、
（３）式（１）中の環Ａ、Ｂ、Ｃがそれぞれ式（４）または式（８）である（１）に記載のポルフィラジン色素、
（４）式（１）中のＭはＶＯまたはＣｕである（３）に記載のポルフィラジン色素、
（５）式（１）中、Ｙは炭素数１〜３のアルキレン基であり、Ｚは置換基を有してもよいフタルイミド基又は置換基を有してもよいピペラジノ基である（４）に記載のポルフィラジン色素、
（６）下記式（９）で表されるポルフィラジン色素

(However, A, B and C are all excluding those represented by the above formula (8)), * in the above formulas (2) to (8) represents a binding site, and X represents a lower alkyl group or a lower alkoxy group. Represents an amino group, a nitro group, a halogen group, a hydroxy group, a carboxy group, a sulfonic acid group, or a sulfonamide group, Y represents a divalent crosslinking group, Z represents a sulfonic acid group, a carboxy group, or a primary or secondary amino group. Represents a residue obtained by removing at least one hydrogen on a nitrogen atom of a group or a residue obtained by removing at least one hydrogen on a nitrogen atom of a heterocyclic ring containing nitrogen, and a and b are both average values. A and b are each 0 or more and 12 or less, and the sum of a and b is 0 or more and 12 or less]
(2) The porphyrazine dye according to (1), wherein the rings A, B, and C in the formula (1) are the formula (2), the formula (4), and the formula (8), respectively.
(3) The porphyrazine dye according to (1), wherein rings A, B, and C in formula (1) are each formula (4) or formula (8),
(4) The porphyrazine dye according to (3), wherein M in the formula (1) is VO or Cu,
(5) In formula (1), Y is an alkylene group having 1 to 3 carbon atoms, and Z is a phthalimide group that may have a substituent or a piperazino group that may have a substituent (4). Porphyrazine dyes as described in
(6) Porphyrazine dye represented by the following formula (9)

［式（１）中の環Ａ、Ｂ、Ｃ、がそれぞれ式（４）または式（８）である（ただし、Ａ、Ｂ、Ｃがすべて式（８）であるものを除く）］、
（７）（１）〜（６）の何れか一項に記載のポルフィラジン色素を分散媒中に分散することを特徴とする色素分散組成物、
（８）分散媒がアクリル系粘着組成物であることを特徴とする（７）に記載の色素分散組成物、
（９）（８）に記載の色素分散組成物を塗布してなるシート、
（１０）（８）に記載の色素分散組成物に熱線遮蔽性金属微粒子を含有することを特徴とする色素分散組成物、
（１１）（１０）に記載の熱線遮蔽性金属微粒子が酸化スズ、酸化インジウムまたは酸化亜鉛のいずれかである色素分散組成物、
（１２）（１１）に記載の色素分散組成物を塗布してなるシート、
に関する。

[Rings A, B, and C in Formula (1) are each Formula (4) or Formula (8) (except that A, B, and C are all Formula (8))],
(7) A dye dispersion composition, wherein the porphyrazine dye according to any one of (1) to (6) is dispersed in a dispersion medium,
(8) The pigment dispersion composition according to (7), wherein the dispersion medium is an acrylic pressure-sensitive adhesive composition,
(9) A sheet formed by applying the pigment dispersion composition according to (8),
(10) A dye dispersion composition comprising heat-shielding metal fine particles in the dye dispersion composition according to (8),
(11) A dye dispersion composition in which the heat ray shielding metal fine particles according to (10) are any one of tin oxide, indium oxide, and zinc oxide,
(12) A sheet formed by applying the dye dispersion composition according to (11),
About.

By using the porphyrazine coloring matter of the present invention as a heat ray shielding material, a high visible light transmittance and an excellent heat ray shielding property were obtained, and yellowishness could be suppressed. Thereby, this porphyrazine pigment | dye can be applied to the field | area of a house or a motor vehicle, without impairing design nature.

The present invention will be described in detail. The present invention relates to a porphyrazine dye of the above formula (1), wherein the dye is dispersed in various dispersion media to obtain a dye dispersion composition. Further, the heat-shielding metal fine particles can be contained in the dye dispersion composition. These compositions are characterized by being applicable to heat ray-shielding pressure-sensitive adhesive sheets.

In the formula (1), examples of the aromatic ring in the rings A to C represented by broken lines include one or two nitrogen atoms such as a benzene ring or a naphthalene ring, a pyridine ring, a pyrazine ring, and a pyridazine ring. Examples thereof include nitrogen-containing heteroaromatic rings. In these, the combination of a benzene ring, a pyridine ring, and a naphthalene ring is preferable, and the combination of a pyridine ring and a naphthalene ring is more preferable. The pyridine ring is most preferably the formula (4).

In the formula (1), M represents a hydrogen atom, a metal atom, a metal oxide, a metal hydroxide, or a metal halide. When M is other than a hydrogen atom, the M means that the porphyrin ring in the formula (1) has a so-called central metal. When M is a hydrogen atom, it means that the porphyrin ring has no central metal.

Specific examples of the metal atom in M include, for example, Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Examples include Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, and Bi.

Examples of the metal oxide include VO and GeO. Examples of the metal hydroxide include Si (OH) ₂ , Cr (OH) ₂ , Sn (OH) ₂ , AlOH, and the like. As the metal halide, for _{example, SiCl 2, VCl, VCl 2} , VOCl, FeCl, GaCl, ZrCl, AlCl , and the like. Among these, metal atoms such as Fe, Co, Cu, Ni, Zn, Al, and V, metal oxides such as VO, metal hydroxides such as AlOH, and the like are preferable. More preferred are Cu and VO, with VO being most preferred.

X in the formula (1) represents a lower alkyl group, a lower alkoxy group, an amino group, a nitro group, a halogen group, a hydroxy group, a carboxy group, a sulfonic acid group, or a sulfonamide group. “Lower” in the present invention means 1 to 4 carbon atoms.

Y is a divalent bridging group, such as an alkylene group having 1 to 3 carbon _{atoms, -CO 2 -, - SO 2} -, - SO 2 NH (CH 2) c- ( wherein, c is 0-4 The alkylene group having 1 to 3 carbon atoms and —SO ₂ NH— in which c is 0 are preferable, and the alkylene group having 1 to 3 carbon atoms is more preferable. Z is a sulfonic acid group, a carboxy group, a residue excluding at least one hydrogen on the nitrogen atom of the primary or secondary amino group, or at least one hydrogen on the nitrogen atom of the heterocyclic ring containing nitrogen. For example, a carboxy group, a phthalimide group which may have a sulfonic acid group substituent, a piperazino group which may have a substituent, a piperidino group which may have a substituent, etc. , A carboxy group, a sulfonic acid group and a phthalimide group which may have a substituent are preferable, and a phthalimide group which may have a substituent is preferable. In addition, as a substituent when Z is a phthalimide group which may have a substituent, a piperazino group which may have a substituent, or a piperidino group which may have a substituent, a hydrogen atom, a lower alkyl group , A lower alkoxy group, a substituted amino group, a nitro group, a halogen group and a sulfonic acid group, preferably a hydrogen atom or a halogen group.

In the present invention, the substituted amino group is not particularly limited, and examples thereof include an amino group substituted with a lower alkyl group or a lower alkoxy group. In the present invention, “lower” means 1 to 4 carbon atoms, and the halogen group means Cl, Br, or I.

In the formula (1), a and b are each 0 or more and 12 or less, and the sum of a and b is 0 or more and 12 or less. Preferably, a and b are each 0 or more and 4 or less, and the sum of a and b is 0 or more and 4 or less.

Specific examples of rings A to C, X, Y, and Z and the numbers of a and b in the porphyrazine coloring matter of the present invention represented by the formula (1) are shown in Table 1 below.
The following examples show representative dyes for specifically explaining the dyes of the present invention, and the present invention is not limited to the following examples. In addition, when the nitrogen-containing heteroaromatic rings of rings A to C are represented by the above formulas (2), (3) and (5), there are positional isomers of nitrogen atoms, and a mixture of isomers during dye synthesis. As obtained. Isolation of these isomers is difficult, and it is difficult to identify isomers by analysis. For this reason, it is usually used as a mixture. The pigment | dye of this invention also contains such a mixture. In the present specification, when the structural formula is expressed without distinguishing these isomers, a typical structural formula is described for convenience.

A method for producing the porphyrazine coloring matter of the present invention represented by the formula (1) will be described.
The porphyrazine dye represented by the formula (1) can be synthesized according to a known method disclosed in, for example, International Publication Nos. 2010/143619 and 2010/013455. The porphyrazine dye represented by the formula (1) is a derivative of each of the formulas (2) to (7) used as a reaction raw material when the synthesis is performed by a known nitrile method or the Weiler method. It can also be synthesized by changing the blending ratio with the naphthalic acid derivative. In addition, the compound represented by the formula (1) obtained by the above method is a regioisomer of the substitution position of the nitrogen-containing heteroaromatic ring in rings A to C and the substitution position of the nitrogen atom of the nitrogen-containing heteroaromatic ring. It is also as described in the said well-known literature that it becomes a mixture.
Compound No. 1 in Table 1 3 or No. The compound represented by 18 can be synthesized according to known methods disclosed in, for example, Japanese Patent No. 25077786, International Publication No. 2010/013455, and Japanese Patent No. 3813750.

As a method for dispersing the compound of the formula (1) in a dispersion medium, a conventional method can be used. That is, the compound of the formula (1) and a dispersion medium are mixed in a predetermined ratio, and a dispersant, a surfactant, etc. are added as necessary, and a dispersing device such as a sand mill, attritor, ball mill, homogenizer, roll mill, bead mill, etc. Can be dispersed. Among these, a bead mill is preferable. Further, in the pulverization of the pigment in the bead mill, it is preferable to use beads having a small diameter, and to process under the condition that the pulverization efficiency is increased by increasing the filling rate of the beads. It is preferred to remove the beads.

Although the dispersion medium used for dispersion is not particularly limited, in the present invention, it refers to water, an organic solvent, an adhesive composition, and the like. These dispersion media may be mixed and used as a mixture. Examples of the organic solvent include hydrocarbon solvents (toluene, xylene, hexane, cyclohexane, n-heptane, etc.), alcohol solvents (methanol, ethanol, isopropyl alcohol, butanol, t-butanol, benzyl alcohol, etc.), ketone solvents. (Acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, acetylacetone, etc.), ester solvents (ethyl acetate, methyl acetate, butyl acetate, cellosolve acetate, amyl acetate, etc.), ether solvents (isopropyl ether, methyl cellosolve, butyl cellosolve) 1,4-dioxane, etc.), glycol solvents (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, etc.), glycol ether solvents Diethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.), glycol ester solvents (ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, etc.), glyme solvents (monoglyme, diglyme, etc.), halogenated solvents ( Dichloromethane, chloroform, etc.), amide solvents (N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone), pyridine, tetrahydrofuran, sulfolane, acetonitrile, and dimethyl sulfoxide. Preferred are water, ketone solvents, alcohol solvents, amide solvents, and hydrocarbon solvents, and more preferred are toluene, methyl ethyl ketone, methyl isobutyl ketone, and acetylacetone.

When the dispersion medium is an acrylic pressure-sensitive adhesive composition, it is preferable to use a highly durable acrylic copolymer pressure-sensitive adhesive resin. The acrylic copolymer-based adhesive resin can be usually produced by copolymerization of a main monomer having a low glass transition point and a comonomer having a high glass transition point when formed into a polymer.

The monomer used as the raw material for the acrylic copolymer-based pressure-sensitive adhesive resin is an alkyl acrylate ester having a low glass transition point and a C 2 to C 14 alkyl group or a C 4 to C 16 meta alkyl group. Acrylic acid alkyl ester and a monomer having a glass transition point higher than them and copolymerizable therewith are used.

Examples of the acrylic acid alkyl ester monomer having a low glass transition point when converted into a polymer include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, methoxyethyl acrylate, n-butyl actylate, isobutyl acrylate, and secondary acrylic acid. Examples thereof include butyl, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, isostearyl acrylate, and the like.

Examples of the methacrylic acid alkyl ester monomer having a low glass transition point when made into a polymer include 2-ethylhexyl methacrylate, n-octyl methacrylate, and n-lauryl methacrylate.

Examples of the copolymerizable monomer include vinyl acetate, acrylonitrile, acrylamide, styrene, methyl methacrylate, methyl acrylate, and the like.

In order to obtain the required adhesion performance in addition to the above monomers, (meth) acrylic acid, itaconic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, acrylic as functional group-containing monomers Amide, methylol acrylamide, dimethylacrylamide, glycidyl methacrylate, maleic anhydride and the like are also used.

Moreover, about the molecular weight, it is preferable that the weight average molecular weights of an acrylic adhesive composition are 100,000-1.2 million. More preferably, it is 200,000 to 800,000.

The degree of crosslinking of the polymer material constituting the pressure-sensitive adhesive composition varies depending on various conditions such as the type and composition of the polymer material, and is not particularly limited, but a plasticizer may be added to the polymer material as necessary. As this plasticizer, esters such as phthalic acid ester, trimellitic acid ester, pyromellitic acid ester, adipic acid ester, sebacic acid ester, phosphoric acid triester or glycol ester, process oil, liquid polyether, liquid polyterpene, Other liquid resin etc. are mentioned, Among these, 1 type or 2 types or more can be mixed and used. It is preferable that such a plasticizer has good compatibility with the pressure-sensitive adhesive composition. Moreover, various additives, such as a ultraviolet absorber or antioxidant, can be added to an adhesive composition other than the said plasticizer as needed, for example.

The weight ratio of the compound of formula (1) to the dispersion medium when dispersing is preferably 3 to 500 dispersion medium, more preferably 15 to 100 dispersion medium with respect to 1 of the compound of formula (1). Yes, and most preferably the dispersion medium is 20-50.
Dispersants include fatty acid salts (soap), α-sulfo fatty acid ester salts (MES), alkylbenzene sulfonates (ABS), linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS), alkyl ether sulfates Low molecular weight anionic (anionic) compounds such as salt (AES) and alkyl sulfate triethanol, fatty acid ethanolamide, polyoxyethylene alkyl ether (AE), polyoxyethylene alkylphenyl ether (APE), sorbitol, sorbitan Nonionic compounds, low molecular weight cationic (cationic) compounds such as alkyltrimethylammonium salt, dialkyldimethylammonium chloride, alkylpyridinium chloride, alkylcarboxyl betaine, sulfobetatai Low molecular amphoteric compounds such as lecithin, formalin condensate of naphthalene sulfonate, polystyrene sulfonate, polyacrylate, copolymer salt of vinyl compound and carboxylic acid monomer, carboxymethyl cellulose, polyvinyl alcohol, etc. Typical examples are polymeric water-based dispersants such as polyacrylic acid partial alkyl esters and polyalkylene polyamines, and polymer cationic dispersants such as polyethyleneimine and aminoalkyl methacrylate copolymers. However, as long as it is suitably applied to the particles of the present invention, those having a structure other than the ones exemplified here are not excluded.

The following are known as specific dispersants to be added. Florene DOPA-15B, Floren DOPA-17 (manufactured by Kyoeisha Chemical Co., Ltd.), Solplus AX5, Solplus TX5, Solsperse 9000, Solsperse 12000, Solsperse 17000, Solsperse 20000, Solsperse 21000, Solsperse 24000, Solsperse 26000, Solsperse 27000, Solsperse 28000, Solsperse 32000, Solsperse 35100, Solsperse 54000, Sol Six 250, (manufactured by Nippon Lubrizol Corporation), EFKA4008, EFKA4009, EFKA4010, EFKA4015, EFKA4046, EFKA4047, EFKA4060, EFKA7440E, EFKA7440E , EFKA4400, EFKA4401, EFKA4402, EFKA4403, EFKA4300, EFKA4330, EFKA4340, EFKA6220, EFKA6225, EFKA6700, EFKA6780, EFKA6782, EFKA11503, EFKA8503 Famex L-12 (manufactured by Ajinomoto Fine Techno Co., Ltd.), TEXAPHOR-UV21, TEXAPHOR-UV61 (manufactured by Cognis Japan Co., Ltd.), DisperBYK101, DisperBYK102, DisperBYK106, DisperBYK108, DisperBYK111, DisperBY 116, DisperBYK130, DisperBYK140, DisperBYK142, DisperBYK145, DisperBYK161, DisperBYK162, DisperBYK163, DisperBYK164, DisperBYK166, DisperBYK167, DisperBYK168, DisperBYK170, DisperBYK171, DisperBYK174, DisperBYK180, DisperBYK182, DisperBYK192, DisperBYK193, DisperBYK2000, DisperBYK2001, DisperBYK2020, DisperBYK2025, DisperBYK2050, DisperBYK2070, DisperBYK21 55, DisperBYK2164, BYK220S, BYK300, BYK306, BYK320, BYK322, BYK325, BYK330, BYK340, BYK350, BYK377, BYK378, BYK380N, BYK410, BYK430, BYK430 , Disparon 1860, Disparon 1934, Disparon DA-400N, Disparon DA-703-50, Disparon DA-725, Disparon DA-705, Disparon DA-7301, Disparon DN-900, Disparon NS-5210, Disparon NVI-8514L, Hip Lard ED-152, Hiprad ED- 16, Hiplard ED-251, Hiplard ED-360 (Enomoto Kasei Co., Ltd.), FTX-207S, FTX-212P, FTX-220P, FTX-220S, FTX-228P, FTX-710LL, FTX-750LL, FT 212P, Aftergent 220P, Aftergent 222F, Aftergent 228P, Aftergent 245F, Aftergent 245P, Aftergent 250, Aftergent 251, Aftergent 710FM, Aftergent 730FM, Aftergent 730LL, Aftergent 730LS, Aftergent 750DM, Footage 750FM (manufactured by Neos Co., Ltd.), AS-1100, AS-1800, AS-2000 (manufactured by Toagosei Co., Ltd.), Kaosela 2000, Kato -Sera 2100, KDH-154, MX-2045L, Homogenol L-18, Homogenol L-95, Rheodor SP-010V, Rheodor SP-030V, Rheodor SP-L10, Rheodor SP-P10 (manufactured by Kao Corporation), Evan U103, Cyanol DC902B, Neugen EA-167, BRYSURF A219B, BRYSURF AL (Daiichi Kogyo Seiyaku Co., Ltd.), Megafuck F-477, MegaFuck 480SF, MegaFuck F-482, (DIC Corporation), Sylface SAG503A, Dinol 604 (manufactured by Nissin Chemical Industry Co., Ltd.), SN spurs 2180, SN spurs 2190, SN leveler S-906 (manufactured by San Nopco Co., Ltd.), S-386, S-420 (manufactured by AGC Seimi Chemical Co., Ltd.) Also Can be exemplified.

When the dye dispersion composition of the present invention contains heat ray-shielding metal fine particles, the heat ray-shielding metal fine particles used have small absorption of visible light and have good absorption characteristics from the near infrared part to the far infrared part. Is suitable. As such a thing, the electroconductive metal oxide which has a plasma wavelength in a near-infrared region is mentioned. Specific examples include tin oxide, indium oxide, zinc oxide, tungsten oxide, chromium oxide, and molybdenum oxide. Of these, tin oxide, indium oxide, and zinc oxide that absorb less light in the visible light region are preferable.

In addition, it is very preferable to dope the third component in order to improve the electrical conductivity of these oxides. As the dopant for this, Sb, V, Nb, Ta, etc. are selected for tin oxide, Zn, Al, Sn, Sb, Ga, Ge, etc. are selected for indium oxide, and zinc oxide is used. For this, Al, Ga, In, Sn, Sb, Nb or the like is selected.

As a method for obtaining a dye dispersion composition in which the dispersion medium is an adhesive composition and heat ray shielding metal fine particles are contained, heat ray shielding metal fine particles or near infrared absorbing dyes are used as main ingredients of the acrylic adhesive composition. The desired heat ray-shielding dye-dispersed composition can be obtained by dispersing in a monomer and then polymerizing it. In addition, a dispersion of heat ray shielding metal fine particles is prepared in advance by a known method (Japanese Patent Application No. 2011-203869), mixed with a monomer together with a composition in which a near-infrared absorbing dye is dispersed in an organic solvent, and then the monomer is polymerized. As a result, the target dye-dispersed composition can also be obtained. An even more convenient method is to directly mix a previously prepared dispersion of heat-shielding metal fine particles into a composition in which the pigment of formula (1) is dispersed in a dispersion medium that is an acrylic adhesive composition. It is also possible to obtain a dye dispersion composition.

The dispersion medium is not particularly limited as to the coating method of the pigment dispersion composition using the organic solvent, the adhesive composition or a mixture thereof, or the pigment dispersion composition containing the heat ray-shielding metal fine particles, but a comma coater and a bar coater. A spin coater, a spray coater, a roll coater, a gravure coater, a knife coater or other various coating apparatuses can be used.

The dispersion ratio of the heat ray shielding metal fine particles and the compound of the formula (1) to the acrylic adhesive composition is determined by the coating thickness of the adhesive layer and the shielding performance. Ideally, the optical performance of the film coated with the dye-dispersed composition should be high in visible light transmittance and low in solar radiation transmittance. Therefore, the optical performance is determined.

In general, the coating thickness of the pressure-sensitive adhesive layer is usually 10 to 50 μm in consideration of the followability to the adherend surface, the adhesive strength and the economy, but the fine particles that give the above-mentioned heat ray shielding properties within this range The amount of (heat ray blocking metal fine particles + the compound of formula (1)): resin solid content = 3: 97 to 1: 1 (weight ratio) is preferable.

The present invention will be specifically described with reference to the following examples and comparative examples, but the present invention is not limited thereto. In the examples,% and parts are based on weight unless otherwise specified.

Example 1 (Compound Example No. 1)
A composition obtained by adding 3.0 parts of phthalic anhydride, 11.9 parts of naphthalic anhydride, 29 parts of urea, 0.40 part of ammonium molybdate and 3.5 parts of vanadyl chloride (V) to 120 parts of sulfolane. Was heated to 200 ° C. and reacted at the same temperature for 11 hours. After completion of the reaction, the reaction solution was cooled to 65 ° C., 100 parts of N, N-dimethylformamide (DMF) was added, and the precipitated solid was separated by filtration. The obtained solid was washed with 50 parts of DMF to obtain 20.3 parts of a wet cake. The obtained wet cake was added to 100 parts of DMF, and the resulting composition was heated to 80 ° C. and stirred at the same temperature for 2 hours. The precipitated solid was separated by filtration and washed with 200 parts of water to obtain 18.9 parts of a wet cake. The obtained wet cake was added to 150 parts of water, and the resulting composition was heated to 90 ° C. and stirred at the same temperature for 2 hours. The precipitated solid was separated by filtration and washed with 200 parts of water to obtain 16.1 parts of a wet cake. The obtained wet cake was dried at 80 ° C. 12.3 parts of 1 were obtained. The maximum absorption wavelength of this compound in concentrated sulfuric acid was 943 nm.

Example 2 (Compound Example No. 2)
In the same manner as in Example 1 except that 3.0 parts of phthalic anhydride in Example 1 is changed to 5.9 parts and 11.9 parts of naphthalic anhydride is changed to 7.9 parts. 12.1 parts of 2 were obtained. The maximum absorption wavelength of this compound in concentrated sulfuric acid was 951, 882, and 815 nm.

Example 3 (Compound Example No. 9)
To 120 parts of sulfolane, 3.3 parts of 3,4-pyridinedicarboxylic acid, 7.9 parts of naphthalic anhydride, 29 parts of urea, 0.40 parts of ammonium molybdate and 3.5 parts of vanadyl chloride (V) were obtained. The composition was heated to 200 ° C. and reacted at the same temperature for 11 hours. After completion of the reaction, the reaction solution was cooled to 65 ° C., 100 parts of N, N-dimethylformamide (DMF) was added, and the precipitated solid was separated by filtration. The obtained solid was washed with 200 parts of DMF at 80 ° C. to obtain 20.3 parts of a wet cake. The obtained wet cake was added to 100 parts of DMF, and the resulting composition was heated to 80 ° C. and stirred at the same temperature for 2 hours. The precipitated solid was separated by filtration and washed with 200 parts of water to obtain 40.1 parts of a wet cake. The obtained wet cake was added to 150 parts of water, and the resulting composition was heated to 90 ° C. and stirred at the same temperature for 2 hours. The precipitated solid was separated by filtration and washed with 7.9 parts of water to obtain 35.2 parts of a wet cake. The obtained wet cake was dried at 80 ° C. 10.8 parts of 9 were obtained. The maximum absorption wavelength of this compound in concentrated sulfuric acid was 933 nm.

Example 4 (Compound Example No. 10)
In the same manner as in Example 3 except that 3.3 parts of 3,4-pyridinedicarboxylic acid in Example 3 were changed to 6.7 parts and 11.9 parts of naphthalic anhydride were changed to 7.9 parts. Example No. 11.4 parts of 10 were obtained. The maximum absorption wavelength of this compound in concentrated sulfuric acid was 939, 804, and 711 nm.

Example 5 (Compound Example No. 3)
In 40 parts of polyphosphoric acid (116%), the compound No. obtained in Example 1 was obtained. 3.4 parts of No. 1, 4.9 parts of phthalimide and 1.0 part of paraformaldehyde were added, and the resulting composition was heated to 140 ° C. and reacted at the same temperature for 6 hours. After completion of the reaction, the reaction solution was cooled to 60 ° C. and 100 parts of water was added. The precipitated solid was separated by filtration and washed with water to obtain 34.0 parts of a wet cake.
The obtained wet cake was added to 100 parts of a 10% aqueous potassium hydroxide solution, and the resulting composition was reacted at 50 ° C. for 2 hours. The precipitated solid was separated by filtration and washed with water to obtain 29 parts of a wet cake.
The obtained wet cake was added to 100 parts of DMF, and the obtained composition was reacted at 25 ° C. The precipitated solid was separated by filtration and washed with water to obtain 13.3 parts of a wet cake. The obtained wet cake was dried at 80 ° C. 6.5 parts of 3 were obtained. The maximum absorption wavelength of this compound in concentrated sulfuric acid was 949 nm.

Example 6 (Compound Example No. 11)
In Example 5, the compound No. 1 obtained in Example 1 was used. 1 to 3.4 parts of compound No. 1 obtained in Example 4. Compound No. 10 was changed in the same manner as in Example 5 except for changing to 3.1 parts of No. 10. 5.7 parts of 11 were obtained. The maximum absorption wavelength of this compound in concentrated sulfuric acid was 940 nm.

Example 7 (Dye dispersion composition 1)
To 7 ml of toluene, 0.21 g of the compound of the formula (4) obtained in Example 1 and 0.21 g of the dispersant DisperBYK140 were added, and zirconia beads were further added as crushing beads. Dispersion treatment was performed with a film mix 30-25 type, manufactured by Primics Co., Ltd. The obtained dispersion was centrifuged using a centrifuge (Hitachi Koki Co., Ltd., himac CR18) to obtain a pigment dispersion composition 1.

Examples 8 to 10 (Dye dispersion compositions 2, 3, and 4)
Dye dispersion compositions 2 to 4 were obtained in the same manner as in Example 7, except that the dye in Example 7 was replaced with the compound obtained in Example 2, 3, or 5.

Synthesis example 1 (acrylic adhesive composition)
291 g of n-butyl acrylate and 9 g of acrylic acid are dissolved in 366 g of toluene, 0.15 g of azobisisobutyronitrile is added, and polymerization is carried out at 70 ° C. for 6 hours under a nitrogen stream to produce an acrylic resin copolymer (weight) Average molecular weight: Mw = 320,000) was obtained. This copolymer was diluted with toluene to obtain an acrylic pressure-sensitive adhesive composition having a solid content of 29.36% and a viscosity of 2700 mPas.

Preparation Example 13 of Dye Dispersion Composition in which Dispersion Medium is Mixture of Organic Solvent and Acrylic Adhesive Composition, and Composition Application Sheet
100 parts by weight of the acrylic adhesive composition obtained in Synthesis Example 1 (butyl acrylate: acrylic acid = 97: 3) and 8.1 parts by weight of the pigment dispersion composition 2 obtained in Example 7 were mixed so as to be uniform. It melt | dissolved and the pigment dispersion composition was obtained. Also, this was coated on a release sheet polyester film (one side treated with silicone) (Lintec 3811 thickness: 38 μm) with a comma coater, the coating film was dried, and the release sheet polyester A dye-dispersed composition-coated sheet (thickness: 15 μm) was prepared by covering with a film (one side treated with silicone) (3801, manufactured by Lintec Corporation, thickness: 38 μm).

Examples 14-16
Dye-dispersed composition coated sheets (thickness: 15 μm) 2 to 4 in the same manner as in Example 13 except that the dye-dispersed composition obtained in Example 7 was replaced with the dye-dispersed composition obtained in Examples 8 to 10. Got.

Comparative Example 1
A dye dispersion composition was prepared in the same manner as in Example 7 except that the compound represented by the formula (2) described in Patent Document 1 was used instead of the dye obtained in Example 1, and the dye dispersion composition was obtained in Example 7. A dye-dispersed composition-coated sheet (thickness: 15 μm) was prepared in the same manner as in Example 13 except that this dye-dispersed composition was used instead of the dye-dispersed composition.

Example 17 (Evaluation of dye-dispersed composition-coated sheet)
The composition coated sheets prepared in Examples 13 to 16 and Comparative Example 1 were evaluated. The test method and the evaluation method of the results are described below.

(A) Calculation of transmittance of composition-coated sheet The transmittance spectrum of the composition-coated sheet obtained above was measured using a spectrophotometer (Shimadzu UV-3150), and the transmittance was calculated.

(B) Calculation of total solar energy (Tts) Total solar energy (Tts; Total
(Solar Transmission) is a measure of how much the thermal energy from the sun penetrates the target material, and was calculated by a calculation formula defined in ISO13837. The smaller the calculated numerical value, the smaller the total solar radiation energy, and the higher the heat ray shielding property.

(C) Calculation of b * value of CIE 1976 (L * a * b *) color system The b * value of CIE 1976 (L * a * b *) color system is a numerical value representing the yellow hue of the measurement object. The larger the value, the stronger the yellowness, and the smaller the value, the weaker the yellowness. This b * value was calculated from the transmission spectrum obtained in (a).

In this evaluation, the b * values when the total solar energy (Tts) values indicating the heat ray shielding properties were made the same were compared and summarized in Table 2.

As shown in Table 2, when the pigment | dye of this invention was used, b * value became smaller than the comparative example which shows the same heat ray shielding property, and it turned out that yellowishness is reduced significantly. Although the yellowishness of the composition-coated sheet of Example 14 could not be confirmed visually, it was confirmed that the sheet of Comparative Example 1 was so strong that it could be visually confirmed.

Production Example 1 (heat ray shielding metal fine particle dispersion)
To 70 parts of toluene, 11.2 parts of indium tin oxide, 7.0 parts of acetylacetone, and 1.75 parts of dispersant DisperBYK140 are added, and zirconia beads are further added as pulverized beads. Dispersion treatment was performed using Mix 30-25 type, manufactured by Primics Co., Ltd. Further, the obtained dispersion (heat ray blocking metal fine particle dispersion) was subjected to centrifugal treatment using a centrifuge (Hitachi Koki Co., Ltd. himac CR18).

Production Example 18 of Dye Dispersion Composition Using Organic Solvent, Adhesive Composition or Mixture thereof as Dispersion Medium, or Dye Dispersion Composition Coating Sheet of Dye Dispersion Composition Containing Heat Ray Shielding Metal Fine Particles in These
100 parts by weight of acrylic adhesive A obtained in Synthesis Example 1 (butyl acrylate: acrylic acid = 97: 3), 144 parts of a toluene dispersion of tin-containing indium oxide (ITO) obtained in Production Example 1, Example 7 14.7 parts of the pigment dispersion obtained in 1 above were mixed and dissolved so as to be uniform, and a heat ray shielding adhesive composition was obtained. Also, this was coated on a release sheet polyester film (one side treated with silicone) (Lintec 3811 thickness: 38 μm) with a comma coater, the coating film was dried, and the release sheet polyester A dye-dispersed composition-coated sheet (thickness: 15 μm) was prepared by covering with a film (one side of which was subjected to silicone treatment) (3801 thickness: 38 μm, manufactured by Lintec Corporation).

Comparative Example 2
A dye-dispersed composition-coated sheet (thickness) containing heat ray-shielding metal fine particles in the same manner as in Example 18 except that the dye-dispersed composition prepared in Comparative Example 1 was used instead of the dye-dispersed liquid obtained in Example 7. : 15 μm).

Example 19
The sheets obtained in Example 18 and Comparative Example 2 were evaluated in the same manner as in Example 17. The results are summarized in Table 3.

As shown in Table 3, even when a dye dispersion composition obtained by mixing a heat ray shielding fine metal particle dispersion in a composition in which the porphyrazine dye of (1) was dispersed in a dispersion medium was used, Example 19 Similarly to the evaluation results shown in Fig. 2, the b * value is smaller than that of the dye dispersion composition using the dye represented by the formula (2) described in Patent Document 1, and the presence or absence of heat ray shielding metal fine particles is affected. As a result, it was found that the yellow color was greatly reduced.

The present invention provides a near-infrared-absorbing dye as a heat ray-shielding material that has excellent heat ray shielding ability, little yellowness, and good design properties. Further, the obtained near-infrared absorbing dye can be applied to a heat ray shielding material for a window glass of a house or an automobile, and is extremely valuable in practical use.

Claims (12)

Porphyrazine dye represented by the following formula (1)

[In formula (1), M represents a metal atom, a metal oxide, a metal hydroxide, or a metal halide, or a hydrogen atom, and rings A, B, and C are each independently represented by the following formulas (2) to (8)

(However, A, B and C are all excluding those represented by the above formula (8)), * in the above formulas (2) to (8) represents a binding site, and X represents a lower alkyl group or a lower alkoxy group. Represents an amino group, a nitro group, a halogen group, a hydroxy group, a carboxy group, a sulfonic acid group, or a sulfonamide group, Y represents a divalent crosslinking group, Z represents a sulfonic acid group, a carboxy group, or a primary or secondary amino group. Represents a residue obtained by removing at least one hydrogen on a nitrogen atom of a group or a residue obtained by removing at least one hydrogen on a nitrogen atom of a heterocyclic ring containing nitrogen, and a and b are both average values. A and b are each 0 or more and 12 or less, and the sum of a and b is 0 or more and 12 or less. The porphyrazine dye according to claim 1, wherein the rings A, B, and C in the formula (1) are each the formula (2), the formula (4), or the formula (8). The porphyrazine coloring matter according to claim 1, wherein the rings A, B and C in the formula (1) are each the formula (4) or the formula (8). The porphyrazine coloring matter according to claim 3, wherein M in the formula (1) is VO or Cu. In formula (1), Y is a C1-C3 alkylene group, Z is a phthalimide group which may have a substituent, or a piperazino group which may have a substituent. Porphyrazine pigment. Porphyrazine dye represented by the following formula (9)

[The rings A, B, and C in the formula (1) are respectively the formula (4) and the formula (8) (except that A, B, and C are all the formula (8)). A dye dispersion composition, wherein the porphyrazine dye according to any one of claims 1 to 6 is dispersed in a dispersion medium. The dye dispersion composition according to claim 7, wherein the dispersion medium is an acrylic pressure-sensitive adhesive composition. The sheet | seat formed by apply | coating the pigment dispersion composition of Claim 8. A dye dispersion composition comprising heat-shielding metal fine particles in the dye dispersion composition according to claim 8. A dye dispersion composition, wherein the heat ray shielding metal fine particles according to claim 10 are any of tin oxide, indium oxide and zinc oxide. The sheet | seat formed by apply | coating the pigment dispersion composition of Claim 11.